Photographic processes using a stabilizing composition comprising a glucoside of a phenolic hydroxyl compound



United States Patent 3,287,127 PHOTOGRAPHIC PROCESSES USING A STABILIZ- ING COMPOSITION COMPRISING A GLUCOSIDE OF A PHENOLIC HYDROXYL COMPOUND Samuel Dershowitz, Brookline, Mass., assignor to Polaroid Corporation, Cambridge, Mass., a corporation of Delaware No Drawing. Filed Dec. 28, 1962, Ser. No. 247,868 Claims. (Cl. 96-29) one or more of such steps with respect to each of the others and the product possessing the features, properties and the relation of elements which are exemplified in. the following detailed disclosure, and the scopeof the application of which will be indicated in the claims.

For a fuller understanding of the nature and objects of the invention, reference should be had to the following detailed description.

US. Patent No. 2,983,606, issued to Howard G. Rogers, May 9, 1961, discloses and claims processes wherein dye developers (i.e., compounds which are both dyes and silver halide developing agents) are used to form color transfer images. In such processes, a photosensitive element is exposed to create therein a latent image. The latent image is developed in the presence of a dye developer and an imagewise distribution of unreacted dye developer, from which the positive image may be created, is formed. At least a portion of said unreacted dye developer is transferred to a superposed image-receiving element to create thereon a positive image. The processes are preferably carried out by disposing the dye developer in the photosensitive element prior to exposure, and cansing it to be solubilized therefrom by an alkaline processing liquid which is applied bet-ween the superposed photosensitive element and image-receiving element. As the process proceeds, the exposed silver halide is reduced to metallicsilver and the portions of the dye developer which are oxidized as a result of the silver development, are substantially immobilized in developed areas. At least a portion of the unreacted dye developer is imbibed on a superposed image-receiving layer to create thereon the positive dye image. The positive dye image is preferably viewed by stripping the photosensitive element from the image-receiving layer.

The above-mentioned alkalineprocessing liquid comprises an aqueous solution of an alkali-metal hydroxide, e.g., sodium hydroxide, cesium hydroxide, or potassium hydroxide. p

The image-receiving elements used in such processes generally comprise an opaque "or transparent support coated with an image-receiving layer of a dyeable mateiial which is permeable to the alkaline aqueous processing 3,287,127 Patented Nov. 22, 1966 solution. In the past, film-forming materials such as polyvinyl alcohol, gelatin and nylons (linear polyamides), such as N-methoxymetnyl polyhexamethylene adipamide, have been used as the dyeable mate-rials.

The color 'fastness of the color photographic images produced in such processes, upon prolonged exposure to sunlight, ultraviolet light, etc., often leaves something to be desired. The copending application of Howard G. Rogers, Serial No. 93,309, filed March 6, 1961 (now US. Patent No. 3,239,338, issued March 8, 1966), discloses a borate ion treatment of such color images, when the image-receiving layers comprise at least in part polyvinyl alcohol, polyvinyl alcohol copolymers or derivatives of polyvinyl alcohol having unreacted hydroxyl groups.

It has now been found that good image stability to light, in many instances to a substantially greater degree than by prior art methods, may be obtained. by associating a glucoside of a phenolic hydroxyl with the image dyes. The glucoside of a phenolic hydroxyl may be conveniently applied to the colored image by immersion, swabbing, coating, spraying, flowing, etc. When desired, thesolution may also comprise a film-forming polymer such, for example, as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, ethyl cellulose, nylon, etc., which will serve as a protective surface coating for the image. In addition, the solution may include other stabilizing agents such, for example, as ultraviolet absorbers, the abovenoted borate ions, or anhydroenneaheptitol. In'a preferred embodiment, the glucoside of a phenolic hydroxyl compound. is applied from aqueous solutions. When desired, such aqueous solutions may contain organic solvents such, for example, as methanol, acetone, etc., to provide for rapid drying of the image surface. It has also been found that such protection can be imparted to color images on a wider range of materials used as imagereceiving elements. For example, when the dyeable image-receiving layer comprised gelatin, nylon, gelatinpoly-4-vinylpyridine, etc., enhanced stability of the colored images thereon was" obtained after treatment in accordance with this invention.

The dye developers, from which the images are formed, may also be defined as compounds which contain in the same molecule both the 'chromophoric system of a dye and also a silver halide developing function. By a. silver halide developing function is meant a grouping adapted to develop exposed silver-halide. A preferred silver halide developing function is a hydroquin-onyl group. Other suitable developing functions are o-dihydroxyphenyl radicals. In general, the developing function includes a benzenoid developing function. Numerous examples of representative dye developers are given in the previously mentioned US. Patent No. 2,983,606 and in applications noted therein.

The processes of this invention have been found especially useful in stabilizing transfer images formed from azo and anthraquinone dye developers.

As mentioned above, the stabilizers of this invention are glucosides of phenolic hydroxyls. Such compounds are naturally occurring materials although some have now been synthesized. The sources and physical properties of such compounds are set forth'in the Merck'lndex, 7th edition. 7 V I By the term glucoside of a phenolic hydroxyl is meant a glucoside attached through a phenolic oxygen to the hydroxyl-containing compound.

As examples of glucosides of phenolic hydroxyls useful in the process of this invention, mention may be made of Arbu-lin (hydroquinone-B-D-glucopyrnnoside) $H1OH O'-' uHnOs Sallcin (saligenin-,B-D-glucopyranoside) O l l I 110g O-Co n05 Esculin (6,7-dihydroxycoumarin-G-glucoside) OH OH OCH;

OH OH O Hesperidin (hesperitin-7-rhamn'oglucoslde) Neo-hesperldin O ECU (Rutinose) rro- 011 ll OH 0-CH2 Narlngen (naringenin-7-rhamnoglucoside) Although the compounds illustrated above are natural products, it should be understood that compounds for use 4. glucoside of a phenolic hydroxyl, mention may be made of hydroquinone bis-glucoside: 1

5 HO OH 0 o/ oHfloH HO OH In addition to stabilizing color images by application per se from aqueous solutions, the stabilizers of this invention provide an increased stabilization effect when used in combination with one or more materials such as boric acid and other sources of borate ions in aqueous solutions, as disclosed in the above-noted application of, Howard G. Rogers, a saccharide, e.g., fructose or anhydroenneaheptitol, and the di ortho-toly lguam'dine salt of dicatechol borate. In a particularly useful embodiment of this invention, the glucoside of a phenolic hydroxyl is used in combination with boric acid, and the ,di-orthoabove, the stabilizing compositions of this invention may also contain a film-forming material, e.g., polyvinyl alco-i hol, ethyl cellulose, polyvinylpyrrolidone, nylon, polyethyl methacrylate, 'etc.

compound used will vary wih many factors such, for example, as the original color fastness of the dye developers, the amount of sunlight the colored image will be to 20% when used alone in aqueous solution and l to i 8% of the total composition when ,used in combination with boric acid. However, in addition to solubility problems of the compounds, when used close to the upper limits of concentration, a yellowing of the color image may occur with some of these compounds, particular-1y after extended periods of time which detracts from the esthetic quality of the print. The preferred percentages of arbutin are 4 to 6% when used alone and 5 to 7% when used in combination with boric acid. The preferred ratio of arbutin to boric acid is 2 to 1.

The following nonlimiting examples illustrate the preparation of image-receiving elements for use in the proc-.

esses of the present invention:

Example I A subcoated film support was coated with a 2:1 mixture of polyvinyl alcohol and poly-4-vinylpyridine containing a small amount of l-phenyl 5-mercaptotetrazole.

Example I] A subcoated film support was coated with a 2: l mixture of gelatin and p0ly-4-vinylpyridine containing a small amount of 1-pheny1-5-mercaptotetrazole.

tolylguanidine salt of dicatechol borate. As mentioned The amount of the glucoside of a phenolic hydroxyl within the scope of this invention arevnot limited to those derived from natural sources; synthetic materials may also be used. As an example of a synthetically prepared Example [11 A subcoated film support was coated with a 5 :5zl

E solution of polyvinyl alcohol, p-trimethylammonium benzaldehyde p-toluenesulfonate partial acetal of polyvinyl alcohol and poly-N-met-hoxy-methyl polyhexaimethylene adipamide containing a small amount of l-phenyl- S-mercaptotetrazole.

Example IV A subcoated film support was coated with a solution of poly-N-rnethoxymethyl polyhexamethylene adipamide.

The image-receiving elements prepared in the abovedescribed manner were used in diffusion transfer processes employing multilayer photosensitive elements prepared in a manner similar to that disclosed in the abovementioned US. Patent No. 2,983,606. In general, the photosensitive elements comprised a support carrying a red-sensitive silver halide emulsion stratum, a green-sensii tive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum; said emulsions having dis-- posed in separate alkali-permeable layers behind them, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer. The particular dye developers employed in the photosensitive elements were (1) 1,4 bis [a-methyl-B-(2,5-dihyclroxyphenyl)-ethylaminoJ-anthraquinone (a cyan dye developer), (2) 2 [p (2',5 dihydroxyphenethyl) phenylazo] npropoxy-l-naphthol (a magenta dye developer),- and (3) 1 phenyl 3 n 'hexylcarbamyl 4 [p (hydroquinonyl-ethyD-phenylazo]-5-pyrazolone (a yellow dye developer). Areas of the photosensitive were exposed to (1) blue and green light only, (2) red and blue light only, and (3) red and green light only. After the transfer process, the image-receiving elements were swabbed with the desired stabilizing solution.

The following nonlimiting examples illustrate the preparation of the stabilizing compositions within this invention.

Example V An aqueous solution of arbutin and 6% boric acid was prepared. 3 V 7 Example VI An aqueous solution of 5% arbutin and 3% boric acid was prepared.

Example VII Example VIII ,A 50:50 methanol/water solution was prepared comprising:

7 Example IX A 50:50 methanol/water solution was prepared comprising:

Percent Salicin 6.3

Polyvinylpyrrolidone 10 Boric acid p p 3 Di-ortho-tolylguanidine salt of dic at'echol borate 0.2

Example X An aqueous solution was prepared comprising:

Percent Arbutin 5 Polyvinyl alcohol 10 Boric acid I 2 Diortho-tolylguanidine salt of dicatechol borate 0.2

Example XI A solution was prepared as in Example VIII using 6.25% esoulin in place of arbutin.

Example XII A solution was prepared as in Example VII-I using 6% neohesperidin in place of ambutin.

Example XIII A solution was prepared as in Example VIII using 3% r'utin in place of ar butin.

' Example XIV Percent Esoulin 10 Polyvinylpyrrolidone 10 Boric acid 6 Di-ortho-t olylguanidine salt of dicatechol borate 0.2

The effectiveness of the processes of this invention was shown by (1) measuring, by reflectance, the integral densities of the transfer images using a green filter, (2) subjecting the images to an accelerated fading test in which the images were-exposed (over saturated NaOl) to a xenon arc, and (3) again measuring the integral densities after 20, 40'and 100 hours of exposure to the xenon are to show the percentage of magenta fading. The test procedureinvolvedapplyin-gthe composition to the image- Percent receiving-elementimrnediately after the formation of the Arbutin 6 a imageand swabbing another image receiva'ng element Polyvinylpyrrolidone 10 approximately 4 hours after exposure. The results ap- Boric acid 3 pear in tabular'form below-in comparison with a water Di-ortho-tolylg'uanidine salt of dicateehol borate 0.2 swab. r

Percent Fading Image- Receiving Swabbing Composition Immediate Delayed Swab,

Element Swab, Hours Hours of (Example of Exposure Exposure Water Swab 56 45 71 94 17 31 38 30 37 57 31 17 37 26 28 1 39 6.3% Salicin (in water) 17 27 63 22 42 86 3% Naringen (in water) 26 40 49 33 58 71 Stp bilizing Composition of Example 13 21 34 20 35 50 Stail iflizing Composition of Example 11 26 34 20- 49 67 Stglfiilizing Composition oi Example 22' 19 20 31 30 2 46 Stabilizing Composition of Example 22 29 27 20 a5 0 a Percent Fading Image- Receiving Swabbing Composition Immediate Delayed Swab,

Element Swab, Hours Hours of (Efiztrgple of Exposure Exposure Stabilizing Composition Example 19 37 39 32 45 63 Stabilizing Composition of Example 2 0 24 1 1 i 50 stgzblillzing Composition of Example 17 62 as so 40 63 st ai uzm Composition of Example 19 26 24 4o 43 stggiIlilzing Composition of Example 14 46 38 3 88 stgiblilliz ing Composition of Example 41 48 33 53 3 58 stgzbilizing Composition of Example 22 52 52 26 39 52 st b gizm Composition of Example 20 2s 47 2a 51 67 6% Arbutin (in water) 14 a0 45 33 47 60 6.3% Salicin (in water)- 5o 64 7s 44 70 so 3% Naringen (in water). 49 76 73 50 77 82 stallliilllizing Composition of Example 36 51 58 42 56 55 stiailili zing Composition of Example 18 65 78 46 73 81 stiazblizzing Composition of Example 62 72 72 62 71 6% Arbutin (in water) 51 72 14 5s 12 71 6.3% Saliein (in water) 73 91 89 77 87 91 Naringen (in water) 4O 79 82 59 82 87 stallizltllizing Composition of Example 52 56 37 49 55 stgbiilizing Composition of Example 42 64 86 4s 61 7a stiagiixl izing Composition of Example 49 63 51 68 72 6% Arbutin (in water) 4s 92 as 62 93 so 6.3% Salicin (in water)--. 96 100 96 98 100 100 3% N aringen (in water) 39 96 61 92 100 96 StgtiiIlIlzing Composition of Example 62 79 82 71 81 79 stlagili zing Composition of Example 84 95 93 85 94 90 stgzbgzlng Composition oi Example 78 91 91 so 91 87 i ggfgg fig In some of the coating compositions, a yellowing of the Yellowed. 7 color image was noted after extended exposure to the a The glucoside of a phenolic hydroxyl compound also xenon are. Where such yellow was especially severe, it can be applied to the color image during processing, Le has been noted 1n the above table Stab1l1z1ng composiby dissolving Said campouud from a layer of flhe film unit t1ons that dld not result in yellowing or resulted in only 1 or by including Said compound in the alkaline processing a low degree of yellowing are lherefore preferred. It composition A swab or other means of application f a should be noted that the protective characteristics of the 1 glucoside of phenolic hydmoxyl compound may or may materials are greater than those that could be attributed not be used in addition to the glucoside in the processing l iq absorption y t1}?! above-described l composition' An example f Such an aqueous Processing mg condition of the colored image. Other phenomena composition i 50 such as color change other than that due to the magenta 1 Percent fading have been noted in the above table to indicate Sodium hydroxide 1 5 17 aberrations in the reported data.- Hydromethyl cellulose 5 It should be noted that the above-described wet xenon Benzotriazole 23 are test is an extremely severe test used as a rapid indica- Nbmzybwpioolinium bromide 3 non of the stabihzmg characteristics of the various com- Sodium thi lf t 1 15 posltions. A factor inherent m such a test mustbe noted: Amutin 2 the age off tlllie lagngp eledment, which ytv1ll t deltlermitne tilef 13- tensltyotei t-an osomeexen, eraeo ag gg g gi fig fi ggg yg fi igg mg g fi g 6O ing. Therefore, in order. to determine precisely, eliminatalkali all h dr h (ioxid d ing the lamp vanable, the relative merits of one stabilizlng g g sfg g g i g y e composition over another, the samples are run simultaneously.

ass l g q gf g z gg g i gzfi: It has also been found thatthe stabilizing effects of @3 i 5 ogessinl Sition treatment with the stabilizers and stabilizing compositions 2: g fsig i :fi zi gal gg elemeits 5 of this invention appear to be increased where the transw a ol lneric acid layer i iid disclosed and claimed in the fer Process has q Performed m the presence of a co n liin a lication of Edwin -H Land Serial No quaternary ammomum compound ".N" 5F gfilegpNovember 1 1962 of such picolinium bromide or N-benzyl-a-picolimum bromide, as liquid pmoessing com'positisn oon'tai a glucoside of disclosed in the copending application of Howard G. 1 a phenolic hydroxyl with the above mentioned image- ,Rogers, Serial No. 50,851, filed August 22, 1960 (now ceivimg e of Edwin Land Serial 3 4 is US. Patent No. 3,173,786, lssued March 16, 1965). An dis l d nd claimed in the impending application of increased stabilizing eifect has also been observed where H a G. Rogers, serialNo. 247,864, filed December the transfer process has been eifected in the presence of 28, 1962. l H such a quaternary ammonium compound in combination with a substituted hydroquinone auxiliary silver halide developing agent, particularly 4-methylphenyl-hydroquinone.

Since certain changes may be made in the above product and process without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. In a process of forming a photographic image in color wherein an exposed silver halide emulsion is developed in the presence of a dye developer to provide a predetermined distribution of unoxidized dye developer, said dye developer being a compound which is both a dye and a silver halide developing agent, and wherein at least part of said distribution of said unoxidized dye developer is transferred from said emulsion to a superposed imagereceiving layer to provide a dye image thereon, the improvement which comprises increasing the stability of said dye image by treating said dye images, subsequent to their formation, with a stabilizing composition comprising a glucoside of a phenolic hydroxyl compound.

2. A process as defined in claim 1 wherein said glucoside of a phenolic hydroxyl compound is applied to said image from an aqueous solution.

3. A process as defined in claim 1 wherein said glucoside of a phenolic hydroxyl compound is applied to said image from a methanol-water solution.

4. A process as defined in claim 1 wherein said stabilizing composition contains boric acid.

5. A process as defined in claim 1 wherein said stabilizing composition contains a film-forming material.

6. A process as defined in claim 1 wherein said stabiliz ing composition contains di-ortho-tolylguanidine salt of dicatechol borate.

7. A process as defined in claim 1 wherein said glucoside of a phenolic hydroxyl compound is arbutin.

8. A process as defined in claim 1 wherein said glucoside of a phenolic hydroxyl compound is salicin.

9. A process as defined in claim 1 wherein said glucoside of a phenolic hydroxyl compound is esculin.

10. A process as defined in claim 1 wherein said glucoside of a phenolic hydroxyl compound is neo-hesperidin.

11. A process as defined in claim 1 wherein said glucoside of a phenolic hydroxyl compound is rutin.

12. A process as defined in claim 1 wherein said glucoside of a phenolic hydroxyl compound is naringen.

13. A process as defined in claim 1 wherein said glucoside of a phenolic hydroxyl compound is hesperidin.

14. A process which comprises the steps of permeating an exposed photosensitive element, including a silver halide emulsion, with an alkaline liquid processing composition, providing said composition with a glucoside of a phenolic hydroxyl compound, developing said exposed silver halide emulsion and forming an imagewise distribution of an unoxidized dye developer, and transferring at least a portion of said glucoside of a phenolic hydroxyl and of said dye developer to an image-receiving layer in superposed relationship with said exposed silver halide emulsion.

15. The process as defined in claim 14 wherein said glucoside of a phenolic hydroxyl compound is arbutin.

16. In a process of forming a photographic image in color wherein an exposed silver halide emulsion is developed in the presence of a dye developer to provide a predetermined distribution of unoxidized dye developer, and wherein at least a portion of said dye developer is transferred from said emulsion to a superposed imagereceiving layer to provide a dye image thereon, the improvement which comprises associating a glucoside of a. phenolic hydroxyl compound with said dye image whereby the stability of said dye image is enhanced.

17. The process as defined in claim 16 wherein said image-receiving layer comprises a film-forming material selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol copolymers, derivatives of polyvinyl alcohol having unreacted hydroxyl groups, gelatin and nylon.

18. The process as defined in claim 16 wherein said glucoside of a phenolic hydroxyl compound is arbutin.

19. A photographic dye image comprising a layer containing an imagewise distribution of a dye developer, said dye developer having associated therewith a glucoside of a phenolic hydroxyl compound in a concentration effective to reduce fading of said dye image by exposure to light.

20. A photographic dye image as defined in claim 19, wherein said glucoside of a phenolic hydroxyl compound is arbutin.

References Cited by the Examiner UNITED STATES PATENTS 3,095,302 6/1963 Jeffreys et a1. 9656 3,146,102 8/1964 Weyerts et al 9656 3,239,338 3/1966 Rogers 963 OTHER REFERENCES The Condensed Chemical Dictionary, 6th ed., 1961, Reinhold Publ. Co., pp. 104, 449, 568, 782, 994 and 996.

NORMAN G. TORCHIN, Primary Examiner.

J, T. BROWN, Assistant Examiner. 

1. IN A PROCESS OF FORMING A PHOTOGRAPHIC IMAGE IN COLOR WHEREIN AN EXPOSED SILVER HALIDE EMULSION IS DEVELOPED IN THE PRESENCE OF A DYE DEVELOPER TO PROVIDE A PREDETERMINED DISTRIBUTION OF UNOXIDIZED DYE DEVELOPER SAID DYE DEVELOPER BEING A COMPOUND WHICH IS BOTH A DYE AND A SILVER HALIDE DEVELOPING AGENT, AND WHEREIN AT LEAST PART OF SAID DISTRIBUTION OF SAID UNOXIDIZED DYE DEVELOPER IS TRANSFERRED FROM SAID EMULSION TO A SUPERPOSED IMAGERECEIVING LAYER TO PROVIDE A DYE IMAGE THEREON, THE IMPROVEMENT WHICH COMPRISES INCREASING THE STABILITY OF SAID DYE IMAGE BY TREATING SAID DYE IMAGES, SUBSEQUENT TO THEIR FORMATION, WITH A STABILIZING COMPOSITION COMPRISING A GLUCOSIDE OF A PHENOLIC HYDROXYL COMPOUND. 